WO1997021646A1 - Method for the colouring of ceramic surfaces - Google Patents

Method for the colouring of ceramic surfaces Download PDF

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Publication number
WO1997021646A1
WO1997021646A1 PCT/EP1996/005312 EP9605312W WO9721646A1 WO 1997021646 A1 WO1997021646 A1 WO 1997021646A1 EP 9605312 W EP9605312 W EP 9605312W WO 9721646 A1 WO9721646 A1 WO 9721646A1
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WO
WIPO (PCT)
Prior art keywords
gold
solution
aqueous
dithiosulfatoaurate
temperatures
Prior art date
Application number
PCT/EP1996/005312
Other languages
German (de)
French (fr)
Inventor
Thomas Klein
Thomas Staffel
Lysander Fischer
Richard Walter
Peter Patzelt
Original Assignee
Bk Ladenburg Gmbh Gesellschaft Für Chemische Erzeugnisse
W.C. Heraeus Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bk Ladenburg Gmbh Gesellschaft Für Chemische Erzeugnisse, W.C. Heraeus Gmbh filed Critical Bk Ladenburg Gmbh Gesellschaft Für Chemische Erzeugnisse
Priority to AT96942286T priority Critical patent/ATE216983T1/en
Priority to EP96942286A priority patent/EP0886629B1/en
Priority to DE59609168T priority patent/DE59609168D1/en
Priority to AU11395/97A priority patent/AU1139597A/en
Priority to JP52166997A priority patent/JP2001511760A/en
Priority to US09/077,751 priority patent/US6045859A/en
Publication of WO1997021646A1 publication Critical patent/WO1997021646A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F9/00—Designs imitating natural patterns
    • B44F9/04—Designs imitating natural patterns of stone surfaces, e.g. marble
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

Definitions

  • the present invention relates to a new process for coloring ceramic surfaces using the aqueous solution of a gold compound
  • DD 224026 describes a "pink color body" which has the approximate composition 2 CaCO 3 x SnO 2 x 2 SiO 2 x H 3 BO 3 and contains 0.1-1.5% Cr 2 O 3 as the coloring component
  • a disadvantage of these pigment powders is that they either have to be added to the entire ceramic mass and thus do not allow any patterning or only lie on the surface of the ceramic as a thin layer and thus change the ceramic surface, so that subsequent processing of the surface is not is more possible
  • colloidal gold which is stabilized by tin oxide, gives deep ruby-red to lilac-red colorations (Cassius' gold purple) et al, Keramikgla ⁇ suren, Wiesbaden / Berlin 1988, page 127)
  • gold sulforesinates which, suspended in an organic solvent, are applied to a ceramic surface and fired at 500-800 ° C., result in a thin film of metallic gold which has a typical gold luster (cf. DE -C1-41 22 131)
  • dilute aqueous solutions of gold salts in particular of gold chlorides, such as gold (III) chloride or tetrachloro-gold acid, which is commercially available as monohydrate and trihydrate, for coloring the surfaces of ceramic bodies, such as Use tiles or porcelain.
  • the method which achieves the object is characterized in that the surfaces are treated with an aqueous alkali metal or ammonium dithiosulfatoaurate (I) solution with a gold concentration of 0.1-10% by weight, the water is evaporated and the dithiosulfatoaurate (l) decomposes at temperatures of 300 - 1400 ° C.
  • I aqueous alkali metal or ammonium dithiosulfatoaurate
  • a dithiosulfatoaurate (I) solution with a gold concentration of 0.5-5.0% by weight is preferred for the process.
  • the process has proven particularly useful when the decomposition of the alkali metal or ammonium dithiosulfatoaurate (l) - usually referred to below as thiosulfatoaurate - takes place at temperatures of 800-1200 ° C., in particular 1140 ° C.
  • the aqueous solution of the thiosulphate toaurate can be applied in a customary manner to the ceramic bodies to be colored by spraying, dipping, painting, printing, etc.
  • the ceramic bodies are fired in a suitable oven at a defined temperature at 300-1400 ° C, advantageously at about 800-1200 ° C, and, in particular to produce a pink color, at 1140 ° C, the Burning time is about half an hour to five hours, preferably one to two hours.
  • the thiosulfatoaurate is pyrolyzed by firing and elemental gold is formed in a finely divided form.
  • the size and distribution of the gold particles which is controlled by the firing temperature and burning time, are decisive for the color impression.
  • the color obtained is blue and changes to purple at temperatures of 400 - 1000 ° C to give a pure shade of pink at temperatures of over 1000 ° C.
  • the gold concentration of the thiosulfatoaurate solutions is also important, since below about 0.1% by weight of gold the color impression becomes too pale and above 10% by weight of gold the color impression after firing into one for metallic, amorphous distributed gold with a typical brown color. A range of 0.3-5% by weight of gold in the thiosulfate acid solution is therefore particularly preferred.
  • the alkali metal and ammonium thiosulfato aurate (I) complexes can be pyrolyzed under the same conditions as gold (III) chloride. They are stable against reducing agents such as metallic iron, so that devices - frames, sieves, nozzles - made of iron or iron alloys can be used.
  • the color impression obtained after firing can be reproduced objectively using a La * b * system.
  • L stands for the brightness
  • a * and b * indicate both the hue and the saturation.
  • a * denotes the position on a red-green axis and b * the position on a yellow-blue axis.
  • Solution I is a preparation of water
  • the solution has a gold concentration of 0.6% by weight and a pH of 6.0.
  • Solution II is a preparation of water and 6.0 g / l gold as sodium dithiosulfatoaurate (l) and 40.0 g / l sodium sulfite.
  • Solution II has a gold concentration of 0.6% by weight and a pH of 9.8.
  • Solution III is a preparation of water and 6.0 g / l gold as sodium dithiosulfatoaurate (l), 40.0 g / l sodium sulfite and ammonium hydroxide up to a pH of 11.4.
  • the gold concentration of solution III is 0.6% by weight. Tiles used
  • Table 1 shows the results of color measurements on tiles which were sprayed with two differently composed thiosulphate aurate solutions, solutions I and II, and fired at three different final temperatures for 60 minutes (0.06 g of Thiosulfato-aurate solution applied to 1 cm 2 of tile surface) At the final temperatures of 800 ° C and 1140 ° C, 760 minutes were prebaked at 600 ° C to reduce the thermal stresses, at 400 ° C a total of 300 minutes was burned it can be seen that the color impression changes from low temperatures (blue) to medium temperatures (purple) to high temperatures (pink)
  • the fired tiles were measured with a "Minolta” Chroma Meter CR-200 (absolute measurements, La * b * color system)
  • T2 400 ° C
  • T2 800 ° C
  • T2 1140 ° C
  • Time 2 60 min
  • Time 2 60 mm
  • Time 2 60 min
  • Type 2 tiles have a medium-light basic color
  • the colored ceramic layer has a thickness of approximately 0.5-2 mm, in particular approximately 1 mm, so that it is possible to grind off the roughness of the fragments (approximately 0.3-0.5 mm) and to polish the surface without impairing the color impression.
  • very stable, surface-polished products can be produced.
  • floor tiles with marble effects can be produced, whereby the floor tiles produced are superior to natural marble due to their strength, but on the other hand can be manufactured much cheaper.
  • Thiosulfatoaurate solutions which additionally contain stabilizers, in particular sulfites or thiosulfates, have proven to be particularly useful.
  • Sodium sulfite and a molar ratio of gold to sulfite such as (0.1-3) to 10, preferably such as (0.5-2) to 10, very particularly such as about 1 to 10 in the solution have proven particularly useful.

Abstract

The present invention relates to a method for the colouring of ceramic surfaces. According to said method the surfaces are treated with an aqueous solution of an alkali metal or ammonium dithiosulphatoaurates (I) with a gold concentration of 0.1-10 % by weight, the water is evaporated and the dithiosulphatoaurate (I) is decomposed at temperatures of 300-1400 °C.

Description

Verfahren zum Färben von Keramikoberflächen Process for coloring ceramic surfaces
Gegenstand der vorliegenden Erfindung ist ein neues Verfahren zum Farben von Keramikoberflachen unter Verwendung der wäßrigen Losung einer Goldverbin¬ dungThe present invention relates to a new process for coloring ceramic surfaces using the aqueous solution of a gold compound
Die Herstellung von rosa Farbtonen in der Keramischen Industrie erweist sich als relativ problematisch Üblich ist die Erzeugung von Pigmentfarben, die durch Zu¬ sammensintern von verschiedenartigsten Metalloxiden erzeugt und mit Borsaure als Fließhilfsmittel auf die Keramikoberflache aufgebracht werdenThe production of pink shades in the ceramic industry proves to be relatively problematic. The production of pigment colors is common, which is produced by sintering together a wide variety of different metal oxides and applied to the ceramic surface with boric acid as a flow aid
Beispielsweise ist in DD 224026 ein "Pinkfarbkorper" beschrieben, der die unge¬ fähre Zusammensetzung 2 CaCO3 x SnO2 x 2 SιO2 x H3BO3 besitzt und 0,1 - 1 ,5 % Cr2O3 als farbgebende Komponente enthältFor example, DD 224026 describes a "pink color body" which has the approximate composition 2 CaCO 3 x SnO 2 x 2 SiO 2 x H 3 BO 3 and contains 0.1-1.5% Cr 2 O 3 as the coloring component
Nachteilig bei diesen Pigmentpulvern ist es, daß sie entweder der gesamten Ke¬ ramikmasse zugefugt werden müssen und damit keine Musterung erlauben oder nur als dünne Schicht auf der Oberflache der Keramik aufliegen und damit die Keramikoberflache verandern, so daß eine nachtragliche Bearbeitung der Ober¬ flache nicht mehr möglich istA disadvantage of these pigment powders is that they either have to be added to the entire ceramic mass and thus do not allow any patterning or only lie on the surface of the ceramic as a thin layer and thus change the ceramic surface, so that subsequent processing of the surface is not is more possible
Es ist weiter bekannt, daß kolloidales Gold, welches durch Zinnoxid stabilisiert ist, tief rubinrote bis lilarote Färbungen ergibt (Cassius'scher Goldpurpur) Der Zusatz dieses Goldpurpurs zu Glasern oder Glasuren ergibt entsprechend rubinrot bis lila gefärbte Glaser (Goldrubinglas) und Glasuren (S Stephanov et al , Keramikgla¬ suren, Wiesbaden/Berlin 1988, Seite 127)It is also known that colloidal gold, which is stabilized by tin oxide, gives deep ruby-red to lilac-red colorations (Cassius' gold purple) et al, Keramikgla¬ suren, Wiesbaden / Berlin 1988, page 127)
Es ist ferner bekannt, daß Goldsulforesinate, welche, in einem organischen Lo¬ sungsmittel suspendiert, auf eine keramische Oberflache aufgetragen und bei 500 - 800°C gebrannt werden, einen dünnen Film aus metallischem Gold erge¬ ben welcher einen typischen Goldglanz aufweist (vgl DE-C1-41 22 131 ) Gemäß DE-C1-43 20 072 lassen sich verdünnte wäßrige Lösungen von Gold¬ salzen, insbesondere von Goldchloriden, wie Gold(lll)-chlorid oder Tetrachloro- goldsäure, welche als Monohydrat und Trihydrat handelsüblich ist, zur Einfärbung der Oberflächen von Keramikkörpern, wie Fliesen oder Porzellan, verwenden. Durch Calcinieren der so oberflächlich eingefärbten Keramikkörper wird auf sehr einfache Weise eine rosa bis blaue Färbung erhalten.It is also known that gold sulforesinates, which, suspended in an organic solvent, are applied to a ceramic surface and fired at 500-800 ° C., result in a thin film of metallic gold which has a typical gold luster (cf. DE -C1-41 22 131) According to DE-C1-43 20 072, dilute aqueous solutions of gold salts, in particular of gold chlorides, such as gold (III) chloride or tetrachloro-gold acid, which is commercially available as monohydrate and trihydrate, for coloring the surfaces of ceramic bodies, such as Use tiles or porcelain. By calcining the ceramic bodies colored on the surface in this way, a pink to blue color is obtained in a very simple manner.
Als nachteilig bei diesem Verfahren hat sich herausgestellt, daß die verwendeten Goldsalzlösungen unter den üblichen Lagerungs- und Verarbeitungsbedingungen nicht stabil sind und insbesondere mit metallischen Oberflächen in den verwende¬ ten Vorrichtungen und mit reduzierenden Verunreinigungen oder Additiven unter Bildung von amorphem Gold reagieren, welches als "Schlamm" ausfällt.It has been found to be disadvantageous in this process that the gold salt solutions used are not stable under the usual storage and processing conditions and in particular react with metallic surfaces in the devices used and with reducing impurities or additives to form amorphous gold, which as " Mud "fails.
Es stellte sich daher die Aufgabe, ein neues Verfahren zum Färben, insbesondere Rosafärben, von Keramikoberflächen zu finden, bei dem die Färbung nachträglich in die Oberflächenschicht des keramischen Materials eingebracht werden kann und diese etwa 0,5 - 2 mm tief verfärbt, so daß sowohl eine Musterung als auch eine Bearbeitung der Oberfläche möglich ist. In dem Verfahren soll eine stabile, ungiftige Goldverbindung verwendet werden.It was therefore the task of finding a new process for coloring, in particular pink, ceramic surfaces, in which the coloring can be subsequently introduced into the surface layer of the ceramic material and discolored about 0.5-2 mm deep, so that both patterning and processing of the surface is possible. A stable, non-toxic gold compound is said to be used in the process.
Diese Aufgabe wird durch die im Hauptanspruch wiedergegebenen Merkmale gelöst und durch die in den Unteransprüchen wiedergegebenen Merkmale geför¬ dert.This object is achieved by the features set out in the main claim and promoted by the features set out in the subclaims.
Das die Lösung der Aufgabe darstellende Verfahren ist erfindungsgemäß dadurch gekennzeichnet, daß man die Oberflächen mit einer wäßrigen Alkalimetall- oder Ammoniumdithiosulfatoaurat(l)-Lösung mit einer Gold-Konzentration von 0,1 - 10 Gewichts-% behandelt, das Wasser verdampft und das Dithiosulfatoaurat(l) bei Temperaturen von 300 - 1400°C zersetzt.The method which achieves the object is characterized in that the surfaces are treated with an aqueous alkali metal or ammonium dithiosulfatoaurate (I) solution with a gold concentration of 0.1-10% by weight, the water is evaporated and the dithiosulfatoaurate (l) decomposes at temperatures of 300 - 1400 ° C.
Für das Verfahren wird eine Dithiosulfatoaurat(l)-Lösung mit einer Gold-Konzen¬ tration von 0,5 - 5,0 Gewichts-% bevorzugt. Besonders bewährt hat sich das Verfahren, wenn die Zersetzung des Alkalimetall¬ oder Ammoniumdithiosulfatoaurats(l) - im folgenden meist als Thiosulfatoaurat bezeichnet - bei Temperaturen von 800 - 1200°C, insbesondere 1140°C, erfolgt.A dithiosulfatoaurate (I) solution with a gold concentration of 0.5-5.0% by weight is preferred for the process. The process has proven particularly useful when the decomposition of the alkali metal or ammonium dithiosulfatoaurate (l) - usually referred to below as thiosulfatoaurate - takes place at temperatures of 800-1200 ° C., in particular 1140 ° C.
Bei dem erfindungsgemaßen Verfahren kann die wäßrige Lösung des Thiosulfa- toaurats in üblicher Weise durch Sprühen, Tauchen, Malen, Drucken usw. auf die zu färbenden Keramikkörper aufgetragen werden.In the process according to the invention, the aqueous solution of the thiosulphate toaurate can be applied in a customary manner to the ceramic bodies to be colored by spraying, dipping, painting, printing, etc.
Nach dem Trocknen werden die Keramikkörper in einem geeigneten Ofen bei ei¬ ner definierten Temperatur bei 300 - 1400°C, vorteilhafterweise bei etwa 800 - 1200°C, und, insbesondere zur Erzeugung einer Rosafärbung, bei 1140°C ge¬ brannt, wobei die Brenndauer etwa eine halbe bis fünf Stunden, vorzugsweise ein bis zwei Stunden, beträgt. Durch das Brennen wird das Thiosulfatoaurat pyroly- siert und elementares Gold in feinverteilter Form gebildet. Maßgeblich für den Farbeindruck ist die Größe und die Verteilung der Goldpartikel, welche durch Brenntemperatur und Brenndauer gesteuert wird. Bei Temperaturen von etwa 300 - 400°C ist der erhaltene Farbton blau und geht bei Temperaturen von 400 - 1000°C in lila über, um bei Temperaturen von über 1000°C einen reinen Rosaton zu ergeben. Wichtig ist auch die Gold-Konzentration der Thiosulfatoaurat-Lösun- gen, da unterhalb von etwa 0,1 Gew.-% Gold der Farbeindruck zu blaß wird und oberhalb von 10 Gewichts-% Gold der Farbeindruck nach dem Brennen in einen für metallisches, amorph verteiltes Gold typischen Braunton umschlägt. Bevorzugt wird daher insbesondere ein Bereich von 0,3 - 5 Gewichts-% Gold in der Thiosul- fatoaurat-Lösung.After drying, the ceramic bodies are fired in a suitable oven at a defined temperature at 300-1400 ° C, advantageously at about 800-1200 ° C, and, in particular to produce a pink color, at 1140 ° C, the Burning time is about half an hour to five hours, preferably one to two hours. The thiosulfatoaurate is pyrolyzed by firing and elemental gold is formed in a finely divided form. The size and distribution of the gold particles, which is controlled by the firing temperature and burning time, are decisive for the color impression. At temperatures of around 300 - 400 ° C, the color obtained is blue and changes to purple at temperatures of 400 - 1000 ° C to give a pure shade of pink at temperatures of over 1000 ° C. The gold concentration of the thiosulfatoaurate solutions is also important, since below about 0.1% by weight of gold the color impression becomes too pale and above 10% by weight of gold the color impression after firing into one for metallic, amorphous distributed gold with a typical brown color. A range of 0.3-5% by weight of gold in the thiosulfate acid solution is therefore particularly preferred.
Überraschenderweise lassen sich die Alkalimetall- und Ammoniumthiosulfatoau- rat(l)-Komplexe unter den gleichen Bedingungen pyrolysieren wie Gold(lll)chlorid. Sie sind gegen Reduktionsmittel wie metallisches Eisen stabil, so daß Geräte - Rahmen, Siebe, Düsen - aus Eisen beziehungsweise Eisen-Legierungen verwen¬ det werden können.Surprisingly, the alkali metal and ammonium thiosulfato aurate (I) complexes can be pyrolyzed under the same conditions as gold (III) chloride. They are stable against reducing agents such as metallic iron, so that devices - frames, sieves, nozzles - made of iron or iron alloys can be used.
Der nach dem Brennen erhaltene Farbeindruck kann objektiv mit Hilfe eines La*b*-Systems wiedergegeben werden. In diesem System steht L für die Hellig¬ keit, während a* und b* sowohl den Farbton als auch die Sättigung angeben. a* bezeichnet dabei die Position auf einer Rot-Grün-Achse und b* die Position auf einer Gelb-Blau-Achse.The color impression obtained after firing can be reproduced objectively using a La * b * system. In this system, L stands for the brightness, while a * and b * indicate both the hue and the saturation. a * denotes the position on a red-green axis and b * the position on a yellow-blue axis.
Ausführungsbeispiele für das Verfahren gemäß der ErfindungEmbodiments of the method according to the invention
Eingesetzte LösungenSolutions used
• Lösung. I• solution. I.
Die Lösung I ist eine Zubereitung aus Wasser undSolution I is a preparation of water and
6,0 g/l Gold als Natriumdithiosulfatoaurat(l),6.0 g / l gold as sodium dithiosulfatoaurate (l),
40,0 g/l Natriumthiosulfat,40.0 g / l sodium thiosulfate,
8,0 g/l Dinatriumhydrogenphosphat,8.0 g / l disodium hydrogen phosphate,
8,0 g/l Natriumdihydrogenphosphat,8.0 g / l sodium dihydrogen phosphate,
14,0 g/l Kaliumperoxomonosulfat und14.0 g / l potassium peroxomonosulfate and
8,5 g/l Ethylendiamintetraessigsaure, Tetranatriumsalz.8.5 g / l ethylenediaminetetraacetic acid, tetrasodium salt.
Die Lösung weist eine Gold-Konzentration von 0,6 Gewichts-% und einen pH-Wert von 6,0 auf.The solution has a gold concentration of 0.6% by weight and a pH of 6.0.
Lösung. II:Solution. II:
Die Lösung II ist eine Zubereitung aus Wasser und 6,0 g/l Gold als Natriumdithiosulfatoaurat(l) und 40,0 g/l Natriumsulfit.Solution II is a preparation of water and 6.0 g / l gold as sodium dithiosulfatoaurate (l) and 40.0 g / l sodium sulfite.
Die Lösung II weist eine Gold-Konzentration von 0,6 Gewichts-% und einen pH-Wert von 9,8 auf.Solution II has a gold concentration of 0.6% by weight and a pH of 9.8.
Lösung III:Solution III:
Die Lösung III ist eine Zubereitung aus Wasser und 6,0 g/l Gold als Natriumdithiosulfatoaurat(l), 40,0 g/l Natriumsulfit und Ammoniumhydroxid bis zu einem pH-Wert von 11 ,4.Solution III is a preparation of water and 6.0 g / l gold as sodium dithiosulfatoaurate (l), 40.0 g / l sodium sulfite and ammonium hydroxide up to a pH of 11.4.
Die Gold-Konzentration der Lösung III beträgt 0,6 Gewichts-%. Verwendete FliesenThe gold concentration of solution III is 0.6% by weight. Tiles used
• Villeroy & Boch, dunkelbrennend, 54 x 54 mm (Typ 1)• Villeroy & Boch, dark burning, 54 x 54 mm (type 1)
• Villeroy & Boch, hellbrennend, 45 x 45 mm• Villeroy & Boch, light burning, 45 x 45 mm
• Villeroy & Boch, hellbrennend, 54 x 54 mm (Typ 2)• Villeroy & Boch, light burning, 54 x 54 mm (type 2)
In der folgenden Tabelle 1 sind die Ergebnisse von Farbmessungen an Fliesen wiedergegeben, die mit zwei unterschiedlich zusammengesetzten Thiosulfato- aurat-Losungen, Losungen I und II, besprüht und bei drei verschiedenen End¬ temperaturen 60 Minuten gebrannt wurden (dabei wurden 0,06 g der Thiosulfato- aurat-Losung auf 1 cm2 Fliesenoberflache aufgetragen) Bei den Endtemperaturen von 800°C und 1140°C wurde jeweils bei 600°C 760 Minuten vorgebrannt, um die thermischen Spannungen zu verringern, bei 400°C wurde insgesamt 300 Minuten gebrannt Es zeigt sich, daß sich der Farbeindruck von niederen Temperaturen (blau) zu mittleren Temperaturen (lila) bis zu hohen Temperaturen (rosa) verän¬ dertTable 1 below shows the results of color measurements on tiles which were sprayed with two differently composed thiosulphate aurate solutions, solutions I and II, and fired at three different final temperatures for 60 minutes (0.06 g of Thiosulfato-aurate solution applied to 1 cm 2 of tile surface) At the final temperatures of 800 ° C and 1140 ° C, 760 minutes were prebaked at 600 ° C to reduce the thermal stresses, at 400 ° C a total of 300 minutes was burned it can be seen that the color impression changes from low temperatures (blue) to medium temperatures (purple) to high temperatures (pink)
Die gebrannten Fliesen wurden mit einem "Minolta" Chroma Meter CR-200 ver¬ messen (Absolut-Messungen, La*b*-Farbsystem)The fired tiles were measured with a "Minolta" Chroma Meter CR-200 (absolute measurements, La * b * color system)
Versuch 1 Versuch 2 Versuch 3Trial 1 Trial 2 Trial 3
T1 = 400°C T1 = 600°C T1 = 600°CT1 = 400 ° C T1 = 600 ° C T1 = 600 ° C
T2 = 400°C T2 = 800°C T2 = 1140°CT2 = 400 ° C T2 = 800 ° C T2 = 1140 ° C
Zeit 1 = 240 min Zeit 1 = 360 min Zeit 1 = 360 minTime 1 = 240 min Time 1 = 360 min Time 1 = 360 min
Zeit 2 = 60 min Zeit 2 = 60 mm Zeit 2 = 60 min Time 2 = 60 min Time 2 = 60 mm Time 2 = 60 min
Tabelle 1. Ergebnisse der FarbmessungenTable 1. Results of the color measurements
Figure imgf000008_0001
Figure imgf000008_0001
Zusätzlich wurden Farbmessungen an großen Fliesen vom Typ 2 durchgeführt (Brenntemperatur 1140°C) Hierbei wurden Farbunterschiede der Blindproben festgestellt, die sich auch auf den Farbton der gefärbten Fliesen auswirken Die Fliesen des Typs 2 zeigen eine mittelhelle GrundfarbeIn addition, color measurements were carried out on large Type 2 tiles (firing temperature 1140 ° C). Differences in color were determined for the blank samples, which also affect the color of the colored tiles. The Type 2 tiles have a medium-light basic color
Tabelle 2 Ergebnisse der Farbmessungen an Fliesen vom Typ 2Table 2 Results of the color measurements on type 2 tiles
Figure imgf000008_0002
Figure imgf000008_0002
Überraschenderweise scheint die Natur des Keramikkorpers nur einen geringen Einfluß auf die Färbung zu haben, da sich Fliesen und Porzellanscherben unter gleichen Auftrags- und Brennbedingungen etwa in gleicher Weise färben Wie die Tabelle 2 zeigt, addiert sich jedoch eine eventuelle Grundfarbung des Scherbens zum Farbton Die gefärbte Keramikschicht weist eine Dicke von ungefähr 0,5 - 2 mm, insbeson¬ dere von etwa 1 mm, auf, so daß es möglich ist, Rauhigkeiten der Scherben ab¬ zuschleifen (ca. 0,3 - 0,5 mm) und die Oberfläche zu polieren, ohne den Farbein¬ druck zu beeinträchtigen. Insbesondere bei hart gebrannten Fliesen lassen sich so sehr trittstabiie, oberflächlich polierte Produkte herstellen. Mit entsprechenden Drucktechniken lassen sich beispielsweise Fußbodenplatten mit Marmoreffekten erzeugen, wobei die erzeugten Fußbodenfliesen natürlichem Marmor aufgrund ihrer Festigkeit überlegen sind, andererseits wesentlich preiswerter hergestellt werden können.Surprisingly, the nature of the ceramic body seems to have only a minor influence on the coloring, since tiles and porcelain shards color in approximately the same way under the same application and firing conditions. As Table 2 shows, however, a possible basic color of the body adds to the color The colored ceramic layer has a thickness of approximately 0.5-2 mm, in particular approximately 1 mm, so that it is possible to grind off the roughness of the fragments (approximately 0.3-0.5 mm) and to polish the surface without impairing the color impression. Particularly with hard-fired tiles, very stable, surface-polished products can be produced. With appropriate printing techniques, for example, floor tiles with marble effects can be produced, whereby the floor tiles produced are superior to natural marble due to their strength, but on the other hand can be manufactured much cheaper.
Als besonders brauchbar haben sich Thiosulfatoaurat-Lösungen erwiesen, die zusätzlich noch Stabilisatoren - insbesondere Sulfite oder Thiosulfate - enthalten.Thiosulfatoaurate solutions which additionally contain stabilizers, in particular sulfites or thiosulfates, have proven to be particularly useful.
Besonders bewährt hat sich dabei das Natriumsulfit und ein Molverhältnis von Gold zu Sulfit wie (0,1 - 3) zu 10, vorzugsweise wie (0,5 - 2) zu 10, ganz beson¬ ders wie etwa 1 zu 10 in der Lösung.Sodium sulfite and a molar ratio of gold to sulfite such as (0.1-3) to 10, preferably such as (0.5-2) to 10, very particularly such as about 1 to 10 in the solution have proven particularly useful.
Bestimmung der wirksamen Stabilisator-KonzentrationDetermination of the effective stabilizer concentration
Es wird eine 6 g/l Gold in Form von Natriumdithiosulfatoaurat(l), Na3[Au(S2O3)2], enthaltende wäßrige Lösung hergestellt. Dann werden aliquote Teile der Lösung mit unterschiedlichen Mengen an Natriumsulfit versetzt und jeweils 5 ml der erhal¬ tenen Lösung in ein Reagenzglas gegeben. In jedes Reagenzglas wird ein Eisennagel gelegt. Nach 12 Stunden wird geprüft, aus welchen Lösungen sich Gold abgeschieden hat und welcher Art die Abscheidung ist. Die Konzentration an Gold und Sulfit in den Lösungen, das Molverhältnis von Gold zu Sulfit und die beobachteten Gold-Abscheidungen werden in der Tabelle 3 zusammengefaßt. Tabelle 3An aqueous solution containing 6 g / l gold in the form of sodium dithiosulfatoaurate (1), Na 3 [Au (S 2 O 3 ) 2 ] is prepared. Then aliquots of the solution are mixed with different amounts of sodium sulfite and each 5 ml of the solution obtained is placed in a test tube. An iron nail is placed in each test tube. After 12 hours, it is checked from which solutions gold has separated out and what type of deposition is. The concentration of gold and sulfite in the solutions, the molar ratio of gold to sulfite and the gold deposits observed are summarized in Table 3. Table 3
Figure imgf000010_0001
Figure imgf000010_0001

Claims

Patentansprüche claims
Verfahren zum Farben von Keramikoberflachen unter Verwendung der wäßri¬ gen Losung einer Goldverbindung, dadurch gekennzeichnet, daß man die Ke- ramikoberflachen mit einer wäßrigen Alkalimetall- oder Ammoniumdithiosulfato- aurat(l)-Losung mit einer Gold-Konzentration von 0,1 - 10 Gewιchts-% behan¬ delt, das Wasser verdampft und das Dithιosulfatoaurat(l) bei Temperaturen von 300 - 1400°C zersetztProcess for coloring ceramic surfaces using the aqueous solution of a gold compound, characterized in that the ceramic surfaces are treated with an aqueous alkali metal or ammonium dithiosulfato-aurate (I) solution with a gold concentration of 0.1-10% by weight % treated, the water evaporates and the dithiosulfatoaurate (l) decomposes at temperatures of 300-1400 ° C
Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, daß die Dithio- sulfatoaurat(l)-Losung eine Gold-Konzentration von 0,5 - 5,0 Gewιchts-% auf¬ weist und durch Sprühen, Tauchen, Malen oder Drucken auf die Keramikober¬ flachen aufgebracht wirdA method according to claim 1, characterized in that the dithiosulfatoaurate (I) solution has a gold concentration of 0.5-5.0% by weight and by spraying, dipping, painting or printing onto the ceramic surfaces is applied
Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Zer¬ setzung des Dιthιosulfatoaurats(l) zwischen Temperaturen von 800 - 1200CC, insbesondere bei 1140°C, durchgeführt wirdThe method of claim 1 or 2, characterized in that the comminuted reduction according to the Dιthιosulfatoaurats (l) between temperatures of 800 - 1200 C is performed C., in particular at 1140 ° C,
Verfahren gemäß einem der Ansprüche 1-3, dadurch gekennzeichnet, daß die wäßrige Dιthιosuifatoaurat(l)-Losung zusatzlich einen wasserlöslichen Sta¬ bilisator enthaltMethod according to one of claims 1-3, characterized in that the aqueous Dιthιosuifatoaurat (l) solution additionally contains a water-soluble stabilizer
Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als Stabilisator Natriumsulfit eingesetzt wirdA method according to claim 4, characterized in that sodium sulfite is used as stabilizer
Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß in der wäßrigen Dιthιosulfatoaurat(l)-Losung Gold und Sulfit im Molverhaltnis von (0,1 - 3) zu 10 vorliegenA method according to claim 5, characterized in that gold and sulfite in a molar ratio of (0.1 - 3) to 10 are present in the aqueous dιthiosulfatoaurate (l) solution
Verfahren nach Anspruch 6, dadurch gekennzeichnet daß Gold und Sulfit im Molverhaltnis von (0,5 - 2) zu 10 vorliegen A method according to claim 6, characterized in that gold and sulfite are present in a molar ratio of (0.5 - 2) to 10
8. Verfahren nach einem der Ansprüche 1-7, dadurch gekennzeichnet, daß die wäßrige Dithiosulfatoaurat(l)-Lösung einen pH-Wert von 6,0 - 12 aufweist.8. The method according to any one of claims 1-7, characterized in that the aqueous dithiosulfatoaurate (l) solution has a pH of 6.0 - 12.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die wäßrige Di- thiosulfatoaurat(l)-Lösung einen pH-Wert von 10 - 12 aufweist. 9. The method according to claim 8, characterized in that the aqueous diethiosulfatoaurate (l) solution has a pH of 10-12.
PCT/EP1996/005312 1995-12-12 1996-11-30 Method for the colouring of ceramic surfaces WO1997021646A1 (en)

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AT96942286T ATE216983T1 (en) 1995-12-12 1996-11-30 METHOD FOR COLORING CERAMIC SURFACES
EP96942286A EP0886629B1 (en) 1995-12-12 1996-11-30 Method for the colouring of ceramic surfaces
DE59609168T DE59609168D1 (en) 1995-12-12 1996-11-30 METHOD FOR COLORING CERAMIC SURFACES
AU11395/97A AU1139597A (en) 1995-12-12 1996-11-30 Method for the colouring of ceramic surfaces
JP52166997A JP2001511760A (en) 1995-12-12 1996-11-30 How to color a ceramic surface
US09/077,751 US6045859A (en) 1995-12-12 1996-11-30 Method for the coloring of ceramic surfaces

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GB2328220A (en) * 1997-08-13 1999-02-17 Cerdec Ag Gold-containing nanoporous aluminium oxide membranes
US6607816B1 (en) 1998-08-21 2003-08-19 Graziano Vignali Formulations based on water soluble gold compounds suitable for coloring ceramic manufactured articles

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DE19701080C1 (en) * 1997-01-15 1998-07-02 Bk Giulini Chem Gmbh & Co Ohg Process for coloring ceramic surfaces
US6464765B1 (en) 2000-09-29 2002-10-15 Ferro Corporation Saturated soluble salt slurries for coloring ceramics
US6796733B2 (en) 2000-10-31 2004-09-28 International Imaging Materials Inc. Thermal transfer ribbon with frosting ink layer
US6854386B2 (en) * 2000-10-31 2005-02-15 International Imaging Materials Inc. Ceramic decal assembly
US20060249245A1 (en) * 2000-10-31 2006-11-09 Bernard Balling Ceramic and glass correction inks
US6990904B2 (en) * 2000-10-31 2006-01-31 International Imaging Materials, Inc Thermal transfer assembly for ceramic imaging
ES2275430B1 (en) * 2005-10-27 2008-06-01 Asociacion De Investigacion De Industrias De La Construccion Aidico-Instituto Tecnologico De La Cons COLORING PROCEDURE WITHOUT PIGMENTS AND CHROMATIC HOMOGENEIZATION OF ORNAMENTAL ROCKS, AND DEVICE FOR PUTTING INTO PRACTICE.
US7829162B2 (en) 2006-08-29 2010-11-09 international imagining materials, inc Thermal transfer ribbon

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DE4320072C1 (en) * 1993-06-17 1994-05-11 Benckiser Knapsack Ladenburg Colouring ceramic surface blue, lilac or esp. pink - by treating with aq. soln. of gold salt, drying and firing at suitable temp., suitable for overall colour or pattern prodn.

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GB2328220A (en) * 1997-08-13 1999-02-17 Cerdec Ag Gold-containing nanoporous aluminium oxide membranes
GB2328220B (en) * 1997-08-13 2002-01-09 Cerdec Ag Gold-containing nanoporous aluminium oxide membranes, a process for their production and their use
US6607816B1 (en) 1998-08-21 2003-08-19 Graziano Vignali Formulations based on water soluble gold compounds suitable for coloring ceramic manufactured articles

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AU1139597A (en) 1997-07-03
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ATE216983T1 (en) 2002-05-15
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